CN104854170B - Acrylic acid redispersible polymer powder for non-cementing external process composition - Google Patents

Acrylic acid redispersible polymer powder for non-cementing external process composition Download PDF

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CN104854170B
CN104854170B CN201380063921.6A CN201380063921A CN104854170B CN 104854170 B CN104854170 B CN 104854170B CN 201380063921 A CN201380063921 A CN 201380063921A CN 104854170 B CN104854170 B CN 104854170B
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dry
external process
process composition
rdp
cementing
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CN104854170A (en
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J·J·索布查克
D·M·瓦森
M·D·韦斯特梅耶
W·J·法比尼
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Dow Global Technologies LLC
Rohm and Haas Co
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Dow Global Technologies LLC
Rohm and Haas Co
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    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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Abstract

The present invention provides a kind of water redispersible polymer powder (RDP) that coatings formulation is such as textured for preparing non-cementing external process composition.Non- cementing external process composition and a kind of method with the processing compositions coating surface comprising the RDP are also provided.When the RDP of the present invention is incorporated into external process composition, when in such as external coating preparation of exterior insulation system of processing (EIFS), resulting composition provides improved resistance to incrustation in the case where not losing wet abrasive resistance relative to comprising acrylic based emulsion powder and the preferably conventional texture coatings formulation of acrylic based emulsion.

Description

Acrylic acid redispersible polymer powder for non-cementing external process composition
Technical field
The present invention relates to water redispersible polymer powder.Exactly, the present invention relates to a kind of redispersible polymerization of water Thing powder (RDP), it, which is suitable as additive, is used for outside non-cementing external process composition, such as veining coating, such as multilayer In external coating in wall system.Aqueous external process composition and its dry-mixed presoma comprising the RDP are also provided.Also provide It is a kind of that the aqueous external process composition of the present invention is wherein coated to surface, such as vertical surface, and dry or allow it Dry method.
Background technology
The spray-dried emulsion polymer in the presence of various additives (such as protective colloid and anti-caking agent) can be passed through Obtained a variety of RDP extensively know and are purchased from commercial source in the art.Conventional RDP example and manufacture are this kind of The method of composition includes U.S. Patent No. 5,403,894, U.S. Patent No. 5,739,179, U.S. Patent No. 6,559, No. 236 and those disclosed in U.S. Patent No. 6,624,243.
Multilayer external wall system, such as exterior insulation and system of processing (EIFS) are widely used for business as exterior wall surface and lived In residence building.This kind of multilayer system is routinely prepared by following：Substrate (such as glued board or stone are covered with one layer of insulating materials Cream plate), combined with the cementing priming coat covering insulating material for being embedded with bar-mat reinforcement, and with non-cementing external coating or external process Thing is processed, and it is 0.1cm to 2.5cm that the non-cementing external coating or external process composition, which are generally applied with trowel coated with thickness is formed, Layer.This kind of external process composition not only provides insulation but also serves as the barrier of moisture entrance and provide decoration functions.Cause This, in order to which suitable for outside coating, this kind of external coating or processing compositions are needed with good exterior durability, including good Colour retention, resistance to incrustation, water proofing property and wearability.
Conventional outside processing compositions or veining coating usually contain film forming polymer so that pigment and extender is common It is attached in firm long-lived coating.Therefore, this kind of processing compositions generally with wet mixture form supply because polymer itself with Aqueous solution form is supplied.But, in order to simplify conveying and eliminate the freeze thaw problem associated with fluent material, it polymerize Thing can in a dry form be conveyed and combined with other dried ingredients of processing compositions so that formed can when in use thereto Add the dry-mixed preparation of water.
It is disclosed in outside processing compositions using RDP adhesive compositions in such as EP-A-0721004, it is provided It is a kind of to be used for the RDP compositions of waterproof membrane and coating.RDP includes the polymerization containing carboxyl, hydroxyl, Carboxylamide or amine functional group Thing, and the reactive component after admixture is dispersed in water with polymers functionality formation nonionic key.Containing RDP's Other examples of external process composition can be seen in WO-A-2012/007529 and U.S. Patent No. 6,228,937.
But, although it is favourable that this kind of dry-mixed preparation is provided in terms of conveying, it has been found that with by liquid polymers, example Such as RHOPLEXTM(Tg is+12 DEG C of 100% acrylate copolymer latex to EI-2000, is purchased from Dow Chemical company (the Dow Chemical Company, USA)) (it is specially designed to external process composition and in EIFS external coatings Color fastness and resistance to incrustation are provided in preparation) the veining coating for preparing compares, in this way using commercially available acrylic acid RDP, Such as DRYCRYLTMPrepared by DP-2903 (Tg is+10 DEG C of 100% acrylic acid RDP, is purchased from Dow Chemical company) Texture the performance that coating provides reduction, exactly, resistance to incrustation and/or wet abrasive resistance.
Therefore, it is an object of the present invention to provide a kind of water redispersible polymer powder (RDP), it is being incorporated into outside add When in work composition, such as the external coating preparation of exterior insulation system of processing (EIFS), relative to including acrylic based emulsion powder And the preferably conventional texture coatings formulation of acrylic based emulsion, not losing wet abrasive resistance, (it is considered as outside durable The early stage index of property) in the case of improved resistance to incrustation is provided.Preferably, relative to the routine for including acrylic based emulsion powder Coatings formulation is textured, and even more preferably still relative to those preparations comprising acrylic based emulsion, external process group Compound provides resistance to incrustation and wet abrasive resistance is improved.
The content of the invention
Stated in various aspects of the invention such as appended claims.
According in a first aspect, the present invention provides a kind of redispersible polymer powder (RDP), the redispersible polymer Powder includes the multistage acrylic copolymer containing carboxyl, and it has：Alkali soluble resins outer portion part and one or more inner sections；Into Core agent, the boiling point of the nucleator is 150 DEG C to 500 DEG C and water solubility is 3.5 or less；And deflocculant, wherein When being dispersed in water, one or more described inner sections use fox equation (Fox comprising glass transition temperature (Tg) Equation -40 DEG C to 50 DEG C of acrylic acid (co) polymer, and wherein described alkali soluble resins outer portion part and institute) are calculated as The weight ratio for stating one or more inner sections is 1: 19 to 2: 3.
2. according to the RDP of above the first aspect of the present invention, wherein the alkali soluble resins outer portion part with it is described one or more The weight ratio of individual inner section is 1: 19 to 1: 4, preferably 1: 19 to 3: 17.
3. according to above first aspect or require any one of 2 RDP, wherein the Tg of one or more inner sections It is -20 DEG C to 25 DEG C, preferably -10 DEG C to 20 DEG C.
4. according to the RDP of any one of above first aspect or aforementioned claim, wherein the multistage acrylic copolymer Comprising one or more polyfunctional monomers by polymer solids 0.1wt.% to 2.0wt.% as polymerized unit, preferably its Described in polyfunctional monomer be selected from allyl methacrylate (ALMA), methacryloxypropyl trimethoxy silane (MATS), dimethylacrylate butanediol, acetoacetoxyethyl methacrylate (AAEM) with and combinations thereof.
5. according to the RDP of any one of above first aspect or aforementioned claim, wherein the multistage acrylic copolymer Include one or more chain-transferring agents by polymer solids 0.1wt.% to 1.0wt.%, preferably wherein described chain-transferring agent Selected from n-dodecyl mercaptan (nDDM), mercaptopropionic acid 3- methyl esters (MMP) with and combinations thereof.
6. according to the RDP of any one of above first aspect or aforementioned claim, wherein by total dry weight of the RDP Meter, the deflocculant exists with 2.0wt% to 10.0wt% amount.
7. according to the RDP of any one of above first aspect or aforementioned claim, it further includes the institute by the RDP State total dry weight meter, 3wt.% to 30wt.% anti-caking agent.
8. according to the RDP of any one of above first aspect or aforementioned claim, wherein the nucleator is selected from C3To C10 Alkyl diol ether, phenyl glycol ethers, C3To C10Alkyl diethylene glycol ether, C3To C10Alkylaryl glycol ethers, C3To C10Alkyl virtue Base diethylene glycol ether, C3To C9The C of alkanoic acid3To C10Arrcostab, C3To C9The C of docosandioic acid3To C10Arrcostab, C3To C9The C of alkanoic acid3 To C10Alkyl diester, C3To C9The C of docosandioic acid3To C10Dialkyl ester and its mixture.
9. according to the RDP of any one of above first aspect or aforementioned claim, wherein the multistage acrylic copolymer Included in combined polymerization form based on the total dry weight for manufacturing the monomer used in the copolymer, 0.1wt.% to middle 20wt.% One or more carboxylic monomers.
According to second aspect, the present invention provides a kind of non-cementing dry-mixed preparation for external process composition, described Dry-mixed preparation includes the gross weight meter by the dry preparation, and 40wt.% to 80wt.% aggregate material and 3wt.% are arrived 30wt.% RDP according to the first aspect of the invention.
11. non-cementing dry-mixed preparation according to the second aspect of the invention, it further includes one or more pigment, its In press the dry-mixed preparation gross weight meter, the pigment with no more than 10wt.% amount exist.
According to the third aspect, the present invention provides a kind of non-cementing external process composition, and it includes the according to the present invention The dry-mixed preparation and water of two aspects.
13. non-cementing external process composition according to the third aspect of the invention we, wherein by the drying of the composition Weight meter, the dry-mixed preparation includes one or more pigment in the amount no more than 10wt.%, and wherein described processing group Total pigment volume concentration (PVC) (PVC) content of compound is 60% to 100%.
14. according to the third aspect of the invention we or require any one of 13 external process composition, its be it is outside absolutely External coating in edge and system of processing (EIFS).
According to fourth aspect, the present invention provides a kind of method of use external process composition coating surface, methods described bag Contain：External process composition according to the third aspect of the invention we is coated on said surface；And dry or allow to dry institute State external process composition.
Embodiment
This specification in the whole text in, unless specified otherwise herein, otherwise any the percentage referred to or percentage by weight etc. are according to group The dry weight of compound is represented.In addition, all scopes described in specification are inclusive and can be combined.
Unless otherwise instructed, otherwise all temperature and pressure units are room temperature and normal pressure (STP).All scopes are bags Including property and can be combined.
All phrases comprising round parentheses represent material in included bracket and its any one of be not present or Both.For example, phrase " (methyl) acrylate " includes acrylate and methacrylate in alternative solution.
As used herein, term " acrylic acid " refers to the polymer of the polymerizate comprising monomer mixture, by total monomer Monomer mixture described in solid meter contains any acrylic monomers more than 50wt.%, such as acrylate, methacrylate, (methyl) acrylamide and (methyl) acrylic acid.
As used herein, unless otherwise instructed, otherwise " average grain diameter " of phrase water redispersible polymer powder particle Refer to the particle diameter or full-size of particle in the distribution of powder particle such as by determination of laser light scattering so that in distribution In 50wt.% particle be less than the particle and the 50wt.% in distribution particle and be more than the particle.For dividing again Shot, uses CoulterTMThe granularmetric analysis devices of LS 230 (sub- Beckman Coulter Inc. of California mine-laying (Beckman Coulter, Brea, CA)), pass through laser defusing measure particle diameter distribution according to manufacturer's recommendation program.With angle Spend and collect particle by laser light scattering and the scattered light of polarization intensity scattering, and be subsequently converted to particle diameter distribution.
As used herein, unless otherwise instructed, otherwise " average grain diameter " of term latex or emulsion particle refers to by dynamic State light scattering uses Brooker Hai Wen instrument companies (Brookhaven Instruments Corporation) 90PLUSTMParticle diameter The weight average particle diameter that analyzer (New York Hall Ci Weier (Holtsville, NY)) is measured according to manufacturer's recommendation.
" glass transition temperature " or " Tg" be using following fox equation [《American Physical Society circulates a notice of》 (Bulletin of the American Physical Society) page 1,3 the 123rd (1956)] calculate copolymer glass Glass conversion temperature：
1/Tg=w1/Tg(1)+w2/Tg(2)
For copolymer, w1And w2Refer to the weight fraction by the two kinds of monomers of monomer weight being fitted into reaction vessel, and And Tg(1)And Tg(2)Refer to glass transition temperature of two kinds of corresponding homopolymers in terms of degree Kelvin (degrees Kelvin).For containing There is the polymer of three or more monomers, add extra term (wn/Tg(n)).For purposes of the present invention, the glass of homopolymer Conversion temperature be《Polymer handbook》, compiled by J. Blancs Sverdrup and E.H. Yi Mogute, International Science Press, 1966 (" Polymer Handbook ", edited by J.Brandrup and E.H.Immergut, Interscience Publishers, 1966) the middle temperature reported, unless the publication does not report the T of specific homopolymerg, in this case The T of homopolymergMeasured by differential scanning colorimetric estimation (DSC).In order to by the glass transition temperature of dsc measurement homopolymer, Prepared in the case of ammonia or primary amine are non-existent and maintain homopolymer sample.Homopolymer sample is dried, 120 DEG C are preheating to, soon Speed is cooled to -100 DEG C, and is then heated to 150 DEG C with 20 DEG C/min of speed, while collecting data.Existed using half supreme people's court The midpoint of flex point measures the glass transition temperature of homopolymer.
As used herein, unless otherwise instructed, otherwise phrase " molecular weight " refers to lead to relative to poly- (styrene) reference material Cross the weight average molecular weight measured by gel permeation chromatography (GPC).
As used herein, term " polymer " " refers to the polymerization being made up of one or more different monomers in alternative solution Thing, such as copolymer, terpolymer, quadripolymer, five-membered copolymer, and can be random, block, grafting, sequence Or any one in gradient polymer.Therefore, term " polymer " " includes copolymer and the polymer in the range of it.
As used herein, term " water redispersible polymer powder ", " redispersible polymer powder " and " RDP " is mutual Change and use and refer to the powder containing polymer, it can be easily spread into deionized water is used to manufacture powder to provide The particle diameter distribution of the initial size of latex or emulsion polymer.
As used herein, term " being substantially free of surfactant " means a kind of composition, and it contains by composition Gross weight solid meter is less than 5000ppm surfactants or preferably less than 2500ppm surfactants.
As used herein, term " water solubility " refers to the amount for the given material being visibly dissolved in the water at room temperature, its It is expressed as the gross weight or the percentage of quality of water used.If therefore for example, 5 grams of materials are dissolved in 100 grams of water, then The water solubility of the material is 5%.
Term " non-cementing " refer to be substantially free of react and harden with water produce water-insoluble materials contain calcium silicates The composition of material.As used herein, term " being substantially free of " means the gross weight meter by external process composition, is less than 5wt.%, preferably less than 2wt.% and even more preferably less than 1wt.%.
As used herein, phrase " wt.% " represents weight % and unless specified otherwise herein, otherwise according to dry weight table Show.
The RDP of the present invention includes deflocculant.Preferably, based on RDP total dry weight, RDP, which is included, is in 0.1wt.% to 30wt.% amount, and be more preferably in the deflocculant of 2.0wt.% to 10.0wt.% amount.
Preferably, in order to avoid using excess surface active agent, in the polymerization phase of carboxylic multistage acrylic copolymer Between there is the deflocculant in RDP of at least a portion total amount.In fact, it is preferable that in carboxylic multistage acrylic acid The colloidal stabiliser being included in RDP of the total amount is added during the polymerization of copolymer.Preferably, RDP, which is included, presses monomer solid The gross weight meter of body is in the deflocculant of 0.05wt.% to 15wt.% amount.It is highly preferred that deflocculant with 0.1wt.% to 10wt.%, even more preferably still 2.0wt.% to 4.0wt.% amount addition.Anion and non-ionic surface are lived Property agent might be less that total water redispersible polymer powder solid 0.5wt.% amount be used for polymerize in.
Preferably, the deflocculant for the present invention is selected from：The polyvinyl alcohol of various known molecular amounts and hydrolysis degree (PVOH), such as partial hydrolysis polyvinyl alcohol；Chelating agent, such as edetate；Polyacrylamide；Polyvinylpyrrolidine Ketone；Polysaccharide；Polyvinyl sulfonic acid；Cellulose；Cellulose ether；Polyester；And its mixture.Most preferably deflocculant is PVOH。
The RDP of the present invention includes nucleator.It is at least 150 DEG C, preferably at least 200 DEG C that suitable nucleator, which includes boiling point, And maximum is 500 DEG C, preferably maximum is 400 DEG C, and water solubility is 3.5% or less, preferably 1.0% or less, More preferably 0.5% or less any compound.But, in order to ensure nucleator is in RDP, under RDP treatment conditions into Core agent should not be volatile.Preferably, exist during the polymerization of carboxylic multistage acrylic copolymer total amount in RDP Interior nucleator.Preferably, acrylic copolymer includes 0.1wt.% to 4.0wt.%, and more preferably 0.5wt.% is arrived 3.0wt.%, even more preferably 1.0wt.% to 2.0wt.% nucleator.Preferably in multistage polymer containing carboxy acrylic Combined polymerization first stage during or polymerization with formed alkali soluble resins section before or during include these nucleators.Altogether Nucleator is preferably used during polymerization instead of surfactant to improve redispersibility.
Preferably, nucleator is selected from following：C3To C10Alkyl diol ether；Phenyl glycol ethers, such as ethylene glycol phenyl ether；C3To C10 Alkyl diethylene glycol ether, such as DPG n-butyl ether；C3To C10Alkylaryl glycol ethers, such as ethylene glycol octyl group phenylate；C3Arrive C10Alkylaryl diethylene glycol ether, such as DPG butyl phenylate；C3To C9The C of alkanoic acid3To C10Arrcostab, such as isobutyl dialkylaminobenzoic acid Ester and isobutyric acid branched alkyl ester, such as 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates；C3To C9The C of docosandioic acid3To C10 Arrcostab, such as succinic acid butyl ester；C3To C9The C of alkanoic acid3To C10Alkyl diester, such as propionic acid 2,2- dimethyl -1- Methylethyl -1, Double -2- the methyl esters of 3- glyceryl；And C3To C9The C of docosandioic acid3To C10Dialkyl ester, such as glutaric acid diisobutyl ester, succinic acid two are different Butyl ester, diisobutyl adipate；And its mixture.It is highly preferred that nucleator is selected from isobutyric acid straight or branched alkyl ester.It is suitable The example of the nucleator of conjunction is shown in table 1 below.
Table 1
1The Dow Chemical (Dow Chemical Co., Midland, MI) of available
The present invention RDP include carboxylic multistage acrylic copolymer, its have alkali soluble resins outer portion part and one or Multiple inner sections.Preferably, acrylic copolymer also contains nucleator as described above and/or deflocculant.
Preferably, multistage acrylic copolymer includes the gross weight by the monomer for manufacturing the copolymer with polymerized form Gauge, 0.1wt.% to 20wt.% one or more carboxyl group-containing monomers.It is highly preferred that copolymer is arrived comprising 0.5wt.% 5.0wt.%, even more preferably 1.0wt.% to 3.5wt.% one or more carboxyl group-containing monomers.Suitable carboxyl group-containing monomer bag Include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, acrylic anhydride, methacrylic anhydride, maleic Half ester, maleic anhydride and the itaconic anhydride of dicarboxylic anhydride/fumaric acid/itaconic acid.Preferably, carboxyl group-containing monomer is (methyl) acrylic acid.
Multistage acrylic copolymer includes alkali soluble resins outer portion part and one or more inner sections.When placed in water, it is interior Section is calculated as -40 DEG C to 50 DEG C comprising glass transition temperature (Tg) using fox equation, preferably -30 DEG C to 35 DEG C, More preferably -20 DEG C to 25 DEG C, and even more preferably -10 DEG C to 20 DEG C of acrylic acid (co) polymer.
Alkali soluble resins outer portion part is 1: 19 to 2 than the relative scale of expression according to weight with one or more inner sections: 3.Preferably, the weight ratio of alkali soluble resins outer portion part and one or more inner sections is 1: 19 to 1: 4, is even more preferably arrived at 1: 19 3∶17。
Due to grafting or physical absorption, multistage acrylic copolymer forms core/shell structure, wherein alkali soluble resins in water Section is located at outside polymer particle.Therefore, the carboxyl in copolymer is located at the surface of redispersible copolymer powder particle.Bag Including nucleator helps to ensure to cover the inner section of multistage acryl co-polymer particles with alkali soluble resins and therefore improves core Colloidal stability.In addition, reducing or eliminating the surfactant requirement produced from multistage copolymer allows relatively large particle diameter Alkali soluble resins, the inner section of its acrylic copolymer contributed in colloid-stabilised RDP.
Multistage acrylic copolymer (is such as described in U.S. Patent No. 5,403,894 using conventional emulsions combined polymerization technology In) produce, make an exception as copolymerization to form alkali soluble resins in the presence of nucleator and preferably substantially live without surface Property agent polyblend in carry out.Conventional thermal polymerization, such as persulfate, and/or Redox Initiator can be used Agent, such as peroxide and bisulfites.
In general, two kinds of combined polymerization technologies can be used；And remaining all polymerization stage is comprising more except for one Functional monomer is with common graft polymers section.There is emulsion polymerisation alkene system unsaturated carboxylic acid included in polyfunctional monomer in technology one Or acid anhydrides and one or more non-ionic monomer (such as (methyl) alkyl acrylate, styrene, alkyl-substituted styrene, (methyl) Acrylamide or (methyl) acrylic acid hydroxy alkyl ester) monomer mixture to form alkali soluble resins, with amine base and alkali solubility Resin and the monomer mixture that one or more non-ionic monomers are formed in second stage, by second stage monomer and alkali solubility Resin combination and polymeric monomer intermixture are to form the copolymer of the present invention.It is multifunctional in a variant of this technology Monomer is a part for second stage monomer mixture and the monomer mixture of non-formation alkali soluble resins, and in the alkali of neutralization It polymerize to form inner section polymer in the presence of soluble resin.
The second polymerization technique as described in U.S. Patent No. 4,916,171 is included in breast in the presence of polyfunctional monomer Liquid polymerize the monomer mixture of one or more non-ionic monomers to form inner section polymer and form alkene in subsequent stage It is the monomer mixture of unsaturated carboxylic acid or acid anhydrides and one or more non-ionic monomers and by monomer mixture and inner section group Merge and polyblend is to form copolymer.Simply by the presence of alkali soluble resins section, as addition polyfunctional monomer can be with Combined polymerization additional nonionic monomer segment is to manufacture multistage copolymer.In polymerization, the temperature in each stage can be arrived at 20 DEG C In the range of 105 DEG C, or preferably 50 DEG C to 95 DEG C.
The total solid of one or more nonionics or inner section copolymer can with the gained weight ratio of alkali soluble resins polymer With 19: 1 to 3: 2, or in the range of preferably 19: 1 to 1: 4, or more preferably 19: 1 to 3: 17.In any polymerization, initially Stage can according to conventional methods be formed by seeding polymerization.
Suitable non-ionic monomer for preparing multistage acrylic copolymer can be selected from ethyl acrylate, acrylic acid fourth Ester, 2-EHA, methyl methacrylate, EMA, butyl methacrylate, methylolation (first Base) acrylamide and methyl methacrylamide, (methyl) hydroxy-ethyl acrylate.Non-ionic monomer should be comprising 5wt.% or more Few any hydroxyalkyl or methylolation monomer or amide-containing monomer.Those of ordinary skill in the art know how selection The non-ionic monomer of polymer segments with required Tg is provided.
Suitable polyfunctional monomer can come from：(a) there are many alkene monomers in two or more unsaturated sites, example Such as acrylic acid and allyl ester, methylallyl isocyanurate, vinyl acetate, dicyclopentenyl ester and the crotons ester of methacrylic acid；Divinyl Benzene；(poly-) glycol two (methyl) acrylate, such as dimethacrylate；And poly- (methyl) acrylic acid of polyalcohol Ester, such as trimethylol-propane trimethacrylate；(b) there are two or more can capture the reactive chain tra nsfer of atom Agent, such as trichlorobromomethane, bromofom, carbon tetrachloride and carbon tetrabromide；And (c) has one or more unsaturated sites and one Or multiple hydridization polyfunctional monomers for capturing atom, such as allyl sulfhydrate, methacrylic mercaptan and crotyl mercaptan； The vinyl ethers and vinyl sulfide of cyclenes alcohol and cyclenes mercaptan.It is preferred that polyfunctional monomer include (methyl) allyl acrylate Or (methyl) methallyl acrylate, acrylic acid and methacrylic acid N- methacrylics vinylamide and allyl sulfide Alcohol.The dosage of polyfunctional monomer is by the total monomer weight in using its monomer mixture, and 0.01wt.% is arrived In the range of 5wt.%, or preferably 0.25wt.% to 3.0wt.%.
The RDP of the present invention can include other polymer with the acrylic acid copolymer polymer blends of multistage containing carboxyl.It is this kind of other Polymer can be for example any nonionic (co) polymer, such as polyolefin；Olefin-vinyl base ester, such as ethane-acetic acid ethyenyl Ester；(methyl) alkyl acrylate；Styrene or styrene acrylic copolymer.Based on the total polymer solid in RDP, blend Thing can include 20wt.% to 80wt.%, or preferably 30wt.% to 70wt.%, or more preferably 40wt.% is arrived 60wt.% this kind of nonionic (co) polymer.
The present invention RDP can include following polymer, its be by the total monomer weight for manufacturing copolymer, 0.001wt.% to 5wt.%, or preferably 0.1wt.% to 1.0wt.% silane-group containing monomer, such as γ-methacryloxypropyl Base propyl trimethoxy silicane or vinyl trialkyl oxysilane, or monomer containing Benzophenone, such as addition of vinyl benzene ketone are total to Polymerizate.
Preferably RDP further includes anti-caking agent.If it does, based on RDP total dry weight, what RDP included The total amount of anti-caking agent is 3.0wt.% to 30.0wt.%, preferably 8.0wt.% to 15.0wt.%.Preferably, anti-caking agent Selected from kaolinton, alumina silicate, dolomite, calcium carbonate, dolomite, silicate mineral and its admixture.It is highly preferred that resistive connection Block agent be selected from kaolinton, alumina silicate with and combinations thereof.It is preferred that alumina silicate be MINEXTMTechnical grade No. 16 to No. 60, that is, include Silica, aluminum oxide, iron oxide and sodium oxide molybdena, calcium oxide, the mesh particle diameter of magnesia and sodium oxide molybdena are less than 1.18mm (16 Number), the composition of preferably less than 150 μm (No. 60).
In addition, RDP can include other conventional additives, such as defoamer, its generally with by total solids up to 1.5wt.% amount is present.The other additives that can be used with convention amount include one or more salt (such as CaCl2、MgCl2), monose, Disaccharides, dispersant or super plasticizer.
Preferably, in order to increase the water-redispersible of water redispersible polymer powder, can substantially it dry aqueous Alkali compounds is added before copolymer dispersion.Alkali compounds can be common with every mole before, during or after polymerization Carboxyl in polymers, 0.4 mole or more, preferably 0.5 mole to 2 moles, more preferably 0.6 mole or more of amount adds Plus.Alkali compounds can amount addition with by the pH of aqueous copolymer product regulations to 8.0 or more, or 9.5 or more, Or preferably at least 10.5, and preferably up to 12.5.Alkali compounds can be inorganic alkaline compound, preferably inorganic Strongly alkaline compound, such as alkali metal hydroxide or alkaline earth metal hydroxide, such as calcium hydroxide, magnesium hydroxide, sodium hydroxide Or potassium hydroxide.
The RDP of present invention average grain diameter can be in 50nm to 500nm, preferably 100nm to 400nm, or more preferably In the range of 163nm to 350nm.
Preferably, based on RDP total dry weight, it is present in the total of multistage acrylic copolymer in RDP and nucleator Amount is 40wt.% to 99.9wt.%.It is highly preferred that based on RDP total dry weight, multistage acrylic copolymer and nucleator Total amount be 50wt.% to 96.9wt.%.
The RDP of the present invention can be by drying comprising the acrylic copolymer of multistage containing carboxyl and (if desired) extra colloid Stabilizer and/or the aqueous mixture of any optional components (such as anti-caking agent) are formed.Preferably, aqueous mixture bag is dried Containing spray drying.Spray drying can be carried out in usual spray drying device, while by means of single fluid, two-fluid or multithread Body nozzle or rotating disk atomizer are atomized.In general, air, nitrogen or nitrogen-rich air may be used as dry gas, dry The inlet temperature of gas is usually no more than 200 DEG C, more preferably preferably 110 DEG C to 180 DEG C, 130 DEG C to 170 DEG C.Depend on Equipment, the Tg of resin and required degree of drying, outlet temperature typically can be 45 DEG C to 120 DEG C, preferably 60 DEG C to 90 DEG C. In an example, the viscosity of charging to be spray dried can be adjusted by solids content, to be less than 1000mPas (Brookfield viscosity (Brookfield viscosity) at 20rpm and 23 DEG C), preferably less than 250mPas value.The solids content of admixture to be spray dried presses the gross weight meter of dispersion liquid, typically can be 25 weight % To 60 weight %, preferably 35 weight % to 50 weight %.
The RDP of the present invention serves many purposes.RDP can be used in extensive numerous compositions as functional additive, such as Non- cementing external process composition, is such as used for the veining of exterior insulation and system of processing (EIFS) and optionally colours external coating In preparation.
According on the other hand, the present invention is provided to the non-cementing dry-mixed preparation of external process composition, it includes and pressed The gross weight meter of dry-mixed preparation, 40wt.% to 80wt.% aggregate material and 3wt.% to 30wt.% according to the present invention First aspect RDP.
As used herein, " aggregate material " refers to any of the drying layer surface texture for assigning gained external process composition Material, preferably sand or more preferably contain silica sand.Preferably, based on the dry weight of preparation, aggregate material with 50wt.% to 70wt.% amount is present.
Preferably, dry-mixed preparation further comprises pigment.Pigment can be inorganic pigment, for example titanium, aluminium, cobalt, copper, Iron, chromium, lead, manganese, titanium or tin pigment, or pigment can be organic pigment, such as carbon black.Preferably, pigment is inorganic pigment, more Preferably titanium pigment and most preferably titanium dioxide (TiO2).When it is present, by the gross weight meter of dry-mixed preparation, do It is in the pigment for being no more than 10wt.%, preferably 1wt.% to 10wt.% amount that mixture product, which is preferably included,.
Optionally, dry-mixed preparation of the invention further includes one or more fillers or extender particles.Including this Class filler or extender particles to processing compositions to provide opacity.If it does, preferably with by the dry of preparation Dry weight meter, more preferably 2wt.% to 30wt.%, 4wt.% to 25wt.%, even more preferably still 10wt.% to 15wt.% Amount include filler or extender particles.It is preferred that filler or extender product to be selected from clay, calcium carbonate, silicate (special Not alumina silicate), talcum, dolomite, silicate mineral with and combinations thereof.Most preferably, filler or extender particles are selected from Calcium carbonate, silicate with and combinations thereof.
According on the other hand, the present invention provides the non-cementing external process of a kind of dry-mixed preparation comprising the present invention and water Composition.Preferably, when processing compositions include one or more pigment, total pigment volume concentration (PVC) (PVC) content of composition It is 60% to 100%.In order to avoid query, PVC, wherein V are calculated using following formulaPigmentRepresent the body of the pigment in composition Product, and VAdhesiveRepresent the volume of the polymeric binder in composition
PVC (%)=VPigment/(VPigment+VAdhesive)×100
Preferably, by the gross weight meter of external process composition, external process composition includes 10wt.% to 30wt.% Water.Preferably, external process composition is the external coating in exterior insulation and system of processing (EIFS).
In addition to component described above, external process composition of the invention can include one or more other components. In preferred embodiment, external process composition further includes another, i.e., deflocculant derived from non-RDP.Implement described In example, deflocculant is preferably by based on total polymer solid, no more than 20wt.%, no more than 5wt.%'s Amount is present.It is adapted to preferred colloidal stabiliser as indicated above.
Preferably, external process composition further includes water-repelling agent.It is highly preferred that water-repelling agent is selected from comprising with least 8, the straight or branched alkyl of more preferably at least 12 carbon atoms, the ester of aryl or aralkyl or sulfonate compound, or Its salt, preferably DEXAMETHASONE SODIUM PHOSPHATE, zinc, calcium, potassium or ammonium salt.Even more preferably, water-repelling agent be selected from NaLS (SLS), it is enuatrol, hard Resin acid sodium, neopelex or its zinc, calcium, potassium or ammonium salt.Even more preferably, hydrophobic compound is SLS.In the reality Apply in example, water-repelling agent is preferably by based on total polymer solid, 0.1wt.% to 10wt.%, more preferably by the total of composition Dry weight meter, 0.5wt.% to 7.5wt.% amount is present.
In addition to the above-identified components, external process composition of the invention and dry-mixed preparation can include one or more Kind of conventional additives, such as rheology modifier, thickener, defoamer, adhesion promoter, UV stabilizer (such as benzophenone), preservative, kill Biological agent, mould inhibitor and/or antifreezing agent, it is therein it is all in the art know and available from commercial source.
According on the other hand, the present invention provides a kind of method of use external process composition coating surface, methods described bag Contain：External process composition according to the third aspect of the invention we is coated on said surface；It is dry described with drying or allowing External process composition.
Some embodiments of the present invention now will be only further described in an exemplary manner.Unless specified otherwise herein, otherwise own Ratio, number and percentage are all represented in terms of dry weight, and unless specified otherwise herein, otherwise all components all have good Commercial quality.
As shown in Table 2 below, the multistage acrylic copolymer in following material preparating example is used：
Table 2
Title Composition and source
MOWIOLTM4-88 solution Polyvinyl alcohol (86.7% to 88.7% hydrolysis, MWIt is about 31K (20wt.%)2
PLURONICTM L-31 Epoxy ethane-epoxy propane-epoxyethane block copolymer4
TEXANOLTM 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates3
TRITONTM, 1X-15 Ethylene glycol octyl group phenylate；HLB=1.5
VERSENETM, EDTA, tetrasodium salt1
WINNOFILTM-S It is coated with stearic acid5CaCO3
1The Dow Chemical of available；2The Kuraray u s company of Texas Houston (Kuraray America, Inc., Houston, TX)；3Eastman Chemical (the Eastman of this baud of Tennessee State gold Chemical, Kingsport, TN)；4BASF joint-stock company (the BASF Ag Florham of New Jersey not Lip river Farnham Parker Park, NJ)；5Su Wei advanced functions Materials Co., Ltd (the Solvay Advanced Functional of Texas Houston Materials, Houston, TX)
Example 1- Macroscopic single crystals：Latex A to R each via inverse two-stage method be made, wherein alkali soluble resins be Prepared in the presence of alkali soluble resins before polymeric internal section copolymer.Latex A, C, D, J and K are in many officials using thermal initiator Energy or cross-linking monomer and/or chain-transferring agent etc. are made presence or absence of lower, and emulsion B, E to I and L to R are using oxidation Initiator is reduced to be made.
Latex A：Presented into the 5L reactors equipped with mechanical agitator, thermocouple, condenser and stainless steel charging aperture Enter 473g deionizations (DI) water and be warming up to 85 DEG C.When warm, the monomer emulsions (ME) as shown in table 3 below .1 are used in Under its maximum rate FMI (New York Sai Aose flowmeter Co., Ltd (Fluid Meter Incorporated, Syosset, NY)) pump was transferred in reactor after about 15 minutes.Then extra 35g deionized water rinsings liquid is added to instead Answer device.In the case where temperature of reactor is at 50 DEG C, by sodium sulfoxylate formaldehyde (SSF), the tert-butyl group hydrogen as shown in table 3.1 Three parts of separate aqueous solutions of peroxide (tBHP) and FeSO47H2O are sequentially added to reactor.At 2-3 minutes It is interior to observe exothermic reaction, progressively increased to 90 DEG C after 15 minutes., will be by tBHP and SSF structures after temperature reaches peak value Into two parts of additional agent aqueous solution be added to reactor to reduce residual monomer.After 10 min, obtain aliquot and Analyzed for 372nm (BI90 plus), 222ppm MMA and pH 2.39.Gained latex then with by sodium hydrate aqueous solution and The neutralization agent solution processing that calcium hydroxide is constituted, obtains the slightly soluble copolymer with translucent solution and pH 11.
Table 3.1
After 15 min, as shown in table 3 below .2, addition ammonium persulfate (APS) initiator solution is then distinguished Monomer emulsions 2 (ME2) and ammonium persulfate aqueous solution are gradually added under 30.5g/min and 2.34g/min, and (co-feeding initiator is molten Liquid).The combined feed time is 90 minutes and reaction temperature is maintained between 84-86 DEG C.After these chargings are completed, 35g is gone Ionized water is used to reactor to rinse ME2 and 10g deionized waters for reactor rinse co-feeding initiator.When these punchings When washing lotion is fed into reactor, latex is cooled to 75 DEG C.The tBHP and SSF aqueous solution was fed into latex simultaneously after 20 minutes Latex is cooled to 50 DEG C.At 50 DEG C, by biocide (Luo Xima (ROCIMA) BT2S, the Tao Shi of available Chemical company) it is added to latex and separates latex and analyze：49.20% solid；pH 7.06：164nm average grain diameters (BI90 plus), 17ppm MMA and 44ppm BA.
Emulsion B：Program according to for latex A prepares this emulsion, and difference is that carrying out redox draws Hair process.Exactly, feed-in 473g deionizations (DI) water (about 22 DEG C) and heated up into 5L reactors.At 60 DEG C, such as Monomer emulsions (ME) shown in table 3 below .3 were transferred in reactor under maximum pump rate after about 15 minutes.Then Extra 35g deionized water rinsings liquid is added to reactor., will be such as following table in the case where temperature of reactor is at about 38 DEG C Three parts of sodium sulfoxylate formaldehyde (SSF), tert-butyl hydroperoxide (tBHP) and FeSO47H2O shown in 3.3 Separate aqueous solution is sequentially added to reactor.Exothermic reaction was observed in 2-3 minutes, 67 were progressively increased to after 15 minutes ℃.After temperature reaches peak value, be made up of tBHP and SSF two parts of additional agent aqueous solution are added to reactor residual to reduce Remaining monomer.After 10 min, aliquot is obtained and for 372nm (BI90 plus), 222ppm MMA and pH 2.39 Analysis.Gained latex is then handled with the neutralization agent solution being made up of sodium hydrate aqueous solution and calcium hydroxide, obtains having half The slightly soluble copolymer of clear solution and pH 11.
Table 3.2
Table 3.3
After 15 min, as shown in table 3 below .4, addition ammonium persulfate (APS) initiator solution is then distinguished Monomer emulsions 2 (ME2), ammonium persulfate aqueous solution are gradually added under 26.9g/min, 1.42g/min and 1.51g/min (altogether Initiator feed solution) and sodium metabisulfite (NaMBS) solution (co-feeding activator solution).The combined feed time is 90 points Clock and reaction temperature is maintained between 64-68 DEG C.After these chargings are completed, 35g deionized waters are used to reactor rush Washing ME2 and 10g deionized waters is used to reactor rinse co-feeding initiator.The tBHP and SSF aqueous solution was after 20 minutes Latex is fed into while latex is cooled into 50 DEG C.At 50 DEG C, by 138.5g Mo Weiao (Mowiol) 4-88 (20wt%) water Solution is added to latex.Then, biocide (Luo Xima BT2S, the Dow Chemical of available) is added to Latex and separate latex and analyze：49.91% solid；pH 7.58：141nm average grain diameters (BI90 plus), 21ppm MMA and 214ppm BA.
Table 3.4
Emulsion C：Program according to for latex A prepares this emulsion, and difference is that BA quantity is reduced to 834.5g and MMA quantity increases to 834.5g.Latex data：48.71% solid；pH 7.22：188nm average grain diameters (BI90 Plus), 3ppm MMA and 8ppm BA.
Emulsion D：Program according to for latex A prepares this emulsion, and difference is that BA quantity is reduced to 961.7g and MMA quantity increases to 718.5g.Latex data：48.85% solid；pH 7.12：190nm average grain diameters (BI90 Plus), 2ppm MMA and 11ppm BA.
Emulsion E：Program according to for emulsion B prepares this emulsion, difference be feed-in 80%ME2 it Addition 8.5g allyl methacrylates (ALMA) in backward ME2.Latex data：48.66% solid；pH 7.28：134nm is put down Equal particle diameter (BI90 plus), 2ppm MMA and 30ppm BA.
Emulsion F：Program according to for emulsion B prepares this emulsion, difference be feed-in 80%ME2 it Addition 8.5g methacrylic acid trimethoxy silane base propyl ester (MATS) in backward ME2.Latex data：47.94% solid； 156nm average grain diameters (BI90 plus), 3ppm MMA and 138ppm BA.
Emulsion G：It is prepared according to for the program described in emulsion B, and difference is ME1 and ME2 weight ratio from 3: 17 are changed into 1: 9 and after feed-in 80%ME2, and 8.5g allyl methacrylates (ALMA) are added into ME2.Definitely Say, feed-in 473g deionized waters and 60 DEG C are warming up into 5L reactors.When warm, the monomer breast as shown in table 3.5 Liquid (ME1) was transferred in reactor under maximum pump rate after about 15 minutes.Then by extra 35g deionized water rinsings liquid It is added to reactor.In the case where temperature of reactor is at 38 DEG C, by the sodium sulfoxylate formaldehyde (SSF) as shown in table 3.5, Three parts of separate aqueous solutions of tert-butyl hydroperoxide (tBHP) and FeSO47H2O are sequentially added to reactor. Exothermic reaction is observed in 2-3 minutes, 67 DEG C were progressively increased to after 15 minutes., will be by tBHP after temperature reaches peak value It is added to reactor to reduce residual monomer with the SSF two parts of additional agent aqueous solution constituted.After 10 min, acquisition etc. point examination Sample and analyzed for 372nm (BI90 plus), 222ppm MMA and pH 2.39.Gained latex is then with by sodium hydroxide water The neutralization agent solution processing that solution and calcium hydroxide are constituted, obtains the slightly soluble copolymer with translucent solution and pH 11.
Table 3.5
After 15 min, as shown in table 3 below .6, addition ammonium persulfate (APS) initiator solution is then distinguished Monomer emulsions 2 (ME2), ammonium persulfate aqueous solution are gradually added under 26.0g/min, 1.33g/min and 1.33g/min (altogether Initiator feed solution) and sodium metabisulfite (NaMBS) solution (co-feeding activator solution).The combined feed time is 90 points Clock and reaction temperature is maintained between 64-68 DEG C.After feed-in 80%ME2,8.5g is added into ME2 with stirring ALMA.After these chargings are completed, 35g deionized waters are used for reactor to be used to react to rinse ME2 and 10g deionized waters Device is to rinse co-feeding initiator.The tBHP and SSF aqueous solution was fed into latex after 20 minutes and latex is cooled into 50 simultaneously ℃.At 50 DEG C, by 138.5g, prestige Austria 4-88 (20wt%) aqueous solution is not added to latex.Then by biocide (Luo Xima BT2S, the Dow Chemical of available) it is added to latex and separates latex and analyze：48.63% solid； pH 7.23：174nm average grain diameters (BI90 plus), viscosity (LV 3/60rpm)：870cps, 3ppm MMA and 344ppm BA.
Table 3.6
Emulsion H：Prepare this emulsion using for the program described in emulsion G, difference be feed-in 80%ME2 it Addition 4.25g ALMA in backward ME2.Latex data：48.44% solid；154nm average grain diameters (BI90 plus), 2ppm MMA and 42ppm BA.
Emulsion I：This emulsion is prepared using for the program described in emulsion G, difference is into ME2 to add 8.5g MATS.Latex data：48.44% solid；154nm average grain diameters (BI90 plus), 2ppm MMA and 42ppm BA.
Emulsion J：This emulsion is prepared using for the program described in latex A, difference is ME1 and ME2 weight Than from be changed into 10: 90 at 15: 85 and ALMA is incorporated into ME2.Exactly, the feed-in 473g deionizations (DI) into 5L reactors Water and it is warming up to 85 DEG C.When warm, the monomer emulsions (ME1) as shown in table 3 below .7 are gone through under maximum pump rate It was transferred to through about 15 minutes in reactor.Then extra 35g deionized water rinsings liquid is added to reactor.In temperature of reactor In the case of at 50 DEG C, by the sodium sulfoxylate formaldehyde (SSF) as shown in table 3.7, tert-butyl hydroperoxide (tBHP) with And three parts of separate aqueous solutions of FeSO47H2O are sequentially added to reactor.Exothermic reaction was observed in 2-3 minutes, 90 DEG C were progressively increased to after 15 minutes.It is after temperature reaches peak value, two parts be made up of tBHP and SSF additional agent are water-soluble Liquid is added to reactor to reduce residual monomer.After 10 min, aliquot is obtained and for 372nm (BI90 Plus), 222ppm MMA and pH 2.39 are analyzed.Gained latex is then with being made up of sodium hydrate aqueous solution and calcium hydroxide Agent solution processing is neutralized, the slightly soluble copolymer with translucent solution and pH 11 is obtained.
After 15 min, as shown in table 3 below .8, addition ammonium persulfate (APS) initiator solution is then distinguished Monomer emulsions 2 (ME2), ammonium persulfate aqueous solution are gradually added under 26.0g/min, 1.33g/min and 1.33g/min (altogether Initiator feed solution) and sodium metabisulfite (NaMBS) solution (co-feeding activator solution).The combined feed time is 90 points Clock and reaction temperature is maintained between 64-68 DEG C.After feed-in 40%ME2,4.25g is added into ME2 with stirring ALMA.After these chargings are completed, 35g deionized waters are used for reactor to be used to react to rinse ME2 and 10g deionized waters Device is to rinse co-feeding initiator.The tBHP and SSF aqueous solution was fed into latex after 20 minutes and latex is cooled into 50 simultaneously ℃.At 50 DEG C, by 138.5g, prestige Austria 4-88 (20wt%) aqueous solution is not added to latex.Then, by biocide (Luo Xima BT2S, the Dow Chemical of available) it is added to latex and separates latex and analyze：49.66% solid； pH 7.20：154nm average grain diameters (BI90 plus), 2ppm MMA and 15ppm BA.
Table 3.7
Table 3.8
Emulsion K：Prepare this emulsion using for the program described in latex A, difference be feed-in 80%ME2 it Afterwards, 8.5g MATS are added into ME2.Latex data：48.16% solid；172nm average grain diameters (BI90 plus), 9ppm MMA and 11ppm BA.
Emulsion L：This emulsion is prepared using for the program described in emulsion B, difference is ME2 composition changes For the material presented in table 3 below .9.Latex data：48.44% solid；159nm average grain diameters (BI90 plus), pH： 7.32,4ppm MMA and 17ppm BA.
Table 3.9
ME2 Wt.(g)
Deionized water 555.9
MowiolTM4-88 solution (20wt%) 139.8
NaLS (SLS) 12.9
Butyl acrylate (BA) 927.3
MMA 600.8
Methacrylic acid acetoacetyl ethyl ester (AAEM) 166.9
Emulsion M：Program according to for emulsion B prepares this emulsion, difference be feed-in 80%ME2 it Afterwards, 4.25g butanediol dimethylacrylates (BGDMA) are added into ME2.Latex data：46.97% solid；106nm is averaged Particle diameter (BI90 plus), pH：7.38,36ppm MMA and 81ppm BA.
Emulsion N：Program according to for emulsion G prepares this emulsion, and difference is into ME2 to add monomer Emulsion seed (ME2 seeds) and nDDM.Exactly, feed-in 481g deionizations (DI) water (22 DEG C) into reactor.It is such as following Monomer emulsions (ME1) shown in table 3.10 were transferred in reactor under maximum pump rate after about 15 minutes.Then will Extra 35g deionized water rinsing liquid is added to reactor., will be such as institute in table 3.10 in the case where temperature of reactor is at 22 DEG C Three parts of independent water of sodium sulfoxylate formaldehyde (SSF), tert-butyl hydroperoxide (tBHP) and the FeSO47H2O shown Solution is sequentially added to reactor.Exothermic reaction was observed in 2-3 minutes, 51 DEG C were progressively increased to after 18 minutes.In temperature Degree is reached after peak value, and be made up of tBHP and SSF two parts of additional agent aqueous solution are added to reactor to reduce residual monomer. After 10 min, the latex is then handled with the neutralization agent solution being made up of sodium hydrate aqueous solution and calcium hydroxide, is obtained To the slightly soluble copolymer with translucent solution and pH 11.
After 15 minutes and temperature of reactor are at 51 DEG C, the 232g ME2 as shown in table 3 below .11 are added Ammonium persulfate (APS) initiator solution and aqueous sodium metabisulfite (NaMBS) are then added to reactor.At 2 minutes It is interior to observe exothermic reaction, 68 DEG C were progressively increased in 9 minutes.After temperature reaches peak value, respectively 12.8g/min, Monomer emulsions 2 (ME2), ammonium persulfate aqueous solution are gradually added under 0.74g/min and 0.744g/min, and (co-feeding initiator is molten Liquid) and sodium metabisulfite (NaMBS) solution (co-feeding activator solution).After 10 min, these chargings increase respectively It is added to 19.2g/min, 1.11g/min and 1.11g/min.After extra 10 minutes, these chargings are increased respectively to 25.6g/min, 1.48g/min and 1.48g/min.The combined feed time is 90 minutes and reaction temperature maintains 64-68 DEG C Between.After feed-in 80%ME2,8.5g ALMA are added into ME2 with stirring.After these chargings are completed, 35g is gone Ionized water is used to reactor to rinse ME2 and 10g deionized waters for reactor rinse co-feeding initiator.TBHP and The SSF aqueous solution was fed into latex after 20 minutes and latex is cooled into 50 DEG C simultaneously.At 50 DEG C, by 138.5g not prestige Austria 4- 88 (20wt%) aqueous solution are added to latex.Then by biocide (Luo Xima BT2S, the DOW Chemical of available Company) it is added to latex and separates latex and analyze：48.25% solid；pH 7.14：280nm average grain diameters (BI90 Plus), viscosity (LV 3/60rpm)：184cps, 6ppm MMA and 59ppm BA.
Table 3.10
Table 3.11
Emulsion O：Program according to for emulsion N prepares this emulsion, and difference is to add into ME2 1.45g n-dodecyl mercaptans (nDDM).Latex data：47.66% solid；250nm average grain diameters (BI90 plus), pH： 7.20,13ppm MMA and 145ppm BA.
Emulsion P：Program according to for emulsion N prepares this emulsion, and difference is to add into ME2 4.25g mercaptopropionic acid 3- methyl esters (MMP).Latex data：47.57% solid；228nm average grain diameters (BI90 plus), pH： 7.26, viscosity (LV 3/60rpm)：74cps, 6ppm MMA and 37ppm BA.
Emulsion Q：Program according to for emulsion N prepares this emulsion, and difference is to add into ME2 1.73g mercaptopropionic acid 3- methyl esters (MMP).Latex data：47.96% solid；181nm average grain diameters (BI90 plus), pH： 7.23, viscosity (LV 3/60rpm)：102cps, 4ppm MMA and 223ppm BA.
Emulsion R：Program according to for emulsion N prepares this emulsion, and difference is to add into ME2 0.86g mercaptopropionic acid 3- methyl esters (MMP).Latex data：47.90% solid；136nm average grain diameters (BI90 plus), pH： 7.17,3ppm MMA and 300ppm BA.
Example 2-RDP is synthesized：As indicated by table 5, constituted at ambient temperature with by 6.25g calcium hydroxides and 365g water Aqueous slurry processing example 1 in the 1000g emulsions specified, obtain pH be 10 to 11 and solids content be about 35% breast Liquid.Then use equipped with nozzle (from Illinois favour Spraying System Co., Ltd. (Spray Systems Company, Wheaton, IL) SU4 or SU5) Buddhist nun sieve's atomizer spray drier (Niro Atomizer Spray Dryer) (Mali The Ji Yiai engineering technology company (GEA Process Engineering Inc., Columbia, MD) of Lanzhou Colombia) it is real Test room spray dryer spray drying and neutralize emulsion.Spray drying condition with uncertain tolerance is as shown in table 4 below.
Table 4
Unless regulation, otherwise agglomeration resistance auxiliary agent is not used in all examples.For the rate of recovery as described below and by resistance to heavy The redispersibility of drop property assesses gained free flowing powder.
The rate of recovery,The protective colloid of the powder reclaimed and dry polymer, agglomeration resistance auxiliary agent and spray drying is total The percentage of amount：The acceptable level of the rate of recovery is the ＞ 75wt.% for the total weight of solids being put into drier, and preferably 90wt.%, but it depends on cyclone efficiency.
Sedimentation：Each powder is stirred by using the standard stainless steel agitator under 400rpm and the numerals of IKW RW 20 The powder and water of device (North Carolina state Wilmington (Wilmington, NC)) mixing 50g equal weights carry out redisperse in 30 minutes. Gained pastel additional water, than 90 parts water of 1 part of pastel water down.Sedimentation indicates the dispersion stabilization of aqueous redispersion powders, Wherein optimal sedimentation is 0mm at 24 hours later.Use 0.5mm diameters × 45cm containing mm Yu mL scales through flat modification Length buret carries out analysis by sedimentation.Preferably, level of sedimentation≤30mm.
Table 5
Example Emulsion The rate of recovery Wt.%H2O %ACA Sedimentation
2.1 A 90.0% 2.38% Nothing 10mm 24hr
2.2 B 86.3% 2.55% 13.76% kaolin 10mm 24hr
2.3 C 82% 2.09% Nothing 10mm 24hr
2.4 D 96.0% 2.39% Nothing 15mm 24hr
2.5 E 77.1% 2.58% Nothing 21mm 24hr
2.6 F 96.0% 2.39% Nothing 15mm 24hr
2.7 G 85.7% 1.74% 13.21% kaolin 12mm 24hr
2.8 H 84.1% 1.82% 12.80% kaolin 9mm 24hr
2.9 I 81.8% 2.10% Nothing 40mm 24hr
2.10 J 86.8% 1.69% 15.26% kaolin 23mm 24hr
2.11 K 84.6% 2.30% Nothing 22mm 24hr
2.12 L 92.5% 2.31% Nothing 9mm 24hr
2.13 M 79.80% 2.25% Nothing 34mm 24hr
2.14 N 83.0% 2.38% 17.04% kaolin 22mm 24hr
2.15 O 83.4% 2.01% 12.49% 25mm 24hr
2.16 P 84.7% 2.24% 15.34% kaolin 15mm 24hr
2.17 Q 84.9% 2.21% 15.11% kaolin 9mm 24hr
2.18 R 83.5% 2.15% 16.58% kaolin 15mm 24hr
Example 3- external process compositions：The performance of the veining coating composition of the present invention includes example 2 by comparing Various RDP EIFS external coatings preparation assess.For each test, coloring and line that PVC is 70% or 79% are prepared Physics and chemistry coating composition and analyze.The details of each preparation is as follows：
70%PVC EIFS preparations：Prepare and include following dry-mixed preparation：7.98wt.%15 sand；64.83wt.% 50-30 sand；5.57wt.%DuramiteTM(it is purchased from her Maurice's pigment company (Imerys Pigments, Inc.) CaCO3Extender)；0.60wt.%MetolatTMP 871 (be purchased from German bright mirror (Munzing, Germany) based on new The nonshrink coalescent of pentanediol)；0.12wt.%WalocelTM(cellulose ether for being purchased from Dow Chemical increases 40000PFV Thick dose)；0.30wt.%Attagel 50TM(rheology modifier based on clay for being purchased from BASF)；0.08wt.% 6 denier Neil micro fiber (#6Denier MiniFibers), cuts into about 0.6cm；0.30wt.%AgitanTMP 804 (is purchased from The defoamer of German bright mirror)；4.49wt.%Ti-PureTMR-960 (is purchased from Du Pont (Dupont) TiO2Pigment)； 0.30wt.%BiobanTMIBPC 100 (biocide for being purchased from Dow Chemical)；0.20wt.% PTPPs point The RDP identified above of powder and 15.24wt.%.Coating composition is textured by admixing dry-mixed preparation when in use With based on the dry weight of preparation, prepared by extra 19.84% water.
79%PVC EIFS preparations：In each test, prepare and include following dry-mixed preparation：7.52wt.%15 Sand；61.07wt.%50-30 sand；15.36wt.%DuramiteTM(it is purchased from the CaCO of her Maurice's pigment company3Increment Agent)；0.56wt.%MetolatTMP 871 (the nonshrink coalescent based on neopentyl glycol for being purchased from German bright mirror)； 0.11wt.%WALOCELTM40000PFV (the cellulose ether thickener for being purchased from Dow Chemical)；0.28wt.% Attagel 50TM(rheology modifier based on clay for being purchased from BASF)；0.08wt.% 6 danier micro fibers, cut It is cut into about 0.6cm；0.28wt.%AgitanTMP 804 (defoamer for being purchased from German bright mirror)；4.23wt.%Ti-PureTM R-960 (is purchased from the TiO of Du Pont2Pigment)；0.28wt.%BiobanTMIBPC 100 (is purchased from killing for Dow Chemical Biological agent)；0.19wt.% PTPP dispersant and 10.04wt.% RDP identified above.Texture coating group Compound by admixing dry-mixed preparation and based on the dry weight of preparation, prepared by extra 18.69% water when in use.
The resistance to incrustation (DPUR) of coatings formulation is textured, i.e. external process composition resistance is because of air and water-borne dirt The ability of surface discolouration caused by accumulation, and wet abrasive resistance are analyzed as follows：
Resistance to incrustation (DPUR)：This test measurement is exposed to after model soil in laboratory environment, is permanently embedded The amount of dirt in the surface of processing compositions.Veining and coloring processing compositions described above paints 0.16cm with trowel Thickness is coated onto on aluminium sheet and allows to dry seven days under 25 DEG C of steady temperature and 50% relative humidity.Coated plate is right The ultraviolet radioactive 24 hours in QUV devices (Kui Pa Nellies company (The Q-Panel Company)) is exposed to afterwards, this it Afterwards, remove plate and it is balanced 4 hours under 25 DEG C and 50% relative humidity, then begin to DPUR tests.
Red iron oxide slurry (MAPICOTM422) surface of coated plate is coated to by brush, is then made described Plate under 25 DEG C and 50% relative humidity dry three hours, after this, under flowing water wash plate simultaneously with a small amount of hand cleanser with Nylon scrubbing brush is gently and uniform scratch is until can no longer remove iron oxide.Then in 25 DEG C of temperature and 50% relative humidity The scrubbed coated panel of lower drying at least two hours.It is anti-using 45 ° of Gardner Ka Lejiade (Gardner Colorgard) II Penetrate meter (Maryland State Yin Quan Gardner/Niu Te instruments branch (Gardner/Neotec Instrument Division, Silver Springs, MD)) measure the reflectance readings of scrubbed coated panel and the clean parts do not tested.Obtain each Three cleanings of sample and three non-clean readings, wherein the average value of three readings is used to calculate the reflection retained using following formula Rate %：
The reflectivity % of reservation is used to characterize the DPUR of external process composition, and wherein high reflectance % indicates good Resistance to incrustation.
Wet abrasive resistance：This test measures external process composition to the patience of abrasion and provides the amount of early stage film forming Degree.Veining described above and coloring processing compositions be applied as with trowel 1.6mm wet thickness be coated to 16.5cm × 43.2cm on vinyl foils.Coated thin slice is dried 24 hours or in 40 DEG C and 70% phase under 75 DEG C and 50% relative humidity To drying 48 hour period under humidity.After this, the uncoated ethene from sample edge is cut down.It is accurate to 0.01 gram of record The initial weight of coated thin slice (A), is then attached on aluminium sheet, and coated side upwards, and is placed on wear testing Instrument (Gardner's straight line tester, Gardner laboratory (Gardener Straight Line Tester, Gardener Labs on)).The 10g according to made from ASTM method D2486 and D3450 grinds scouring media (SC-2, Lei Nakesa company (the Lenexa Company)) and 10g water be uniformly coated on brush, the brush is installed on abrasion meter, bristle contact warp The thin slice of coating.Start abrasion meter and complete 2000 circulation, complete it is every 500 circulation after 10g SC-2 and 10g water is coated with brush.Coated thin slice removes tester and rinsed under warm water.Coated thin slice at 25 DEG C and Dried at least 12 hours under 50% relative humidity.After drying, it is accurate to 0.01 gram and determines the final of coated thin slice (B) Weight.Finally, uncoated vinyl foils cut into with three test strips of coated thin slice identical size and 0.01 gram is accurate to weigh.The weight of uncoated vinyl foils (C) is the average value of these three weight.Surveyed according to below equation The weight loss % of fixed coated thin slice, wherein the result recorded represents the average value of at least two test samples：
Weight loss % lower value indicates good initial film forming and wear resistance.
The DPUR results of various veining coatings formulations are summarized in table 6 below .1 to 6.5.In table 6.1 and 6.2, Without using polyfunctional monomer or chain-transferring agent.
Table 6.1：Redox polymerize with thermal initiation
Table 6.2：Copolymer inner section Tg
Table 6.3：Polyfunctional monomer in copolymer inner section
Table 6.4：The weight ratio of alkali soluble resins outer portion part and inner section
Table 6.5：Extra water-repelling agent
*SLS=NaLSs
For the DPUR performances of veining coating and conventional texture coating relatively more of the invention, prepare and include following class Like coatings formulation：Commercially available RDP, i.e. DRYCRYLTMDP-2903 powder (Tg is+10 DEG C of 100% acrylic acid RDP), ELOTEXTMWR8600 powder (multistage cationic polymerization made from the method according to U.S. Patent No. 7,674,860 Thing, it includes butyl acrylate/methylmethacrylate copolymer (Tg-2 DEG C) core section, and the cationic amine containing shell section) with And ELOTEXTMFLEX8300 powder (the acrylic acid (common) that the method according to U.S. Patent No. 7,674,860 is manufactured Polymer RDP)；Or polymer latex, such as RHOPLEXTM(Tg is+12 DEG C of 100% acrylate copolymer to EI-2000 polymer Latex), good DPUR performances are provided in EIFS external coating preparations known to it.These compare veining coatings formulation DPUR results are summarized in table 6 below .6：
Table 6.6：Compare DPUR results
1The Dow Chemical of available；EI-2000 powder is that Tg is+12 DEG C of 100% acroleic acid polymerization Thing latex；DP-2903 powder is that Tg is+10 DEG C of 100% acrylic acid RDP.
2Akzo Nobel's performance chemicalses Elotex AG (AkzoNobel Functional of Switzerland Chemicals Elotex AG, Switzerland).WR 8600 is the side according to U.S. Patent No. 7,674,860 Multistage cationic polymer made from method, it includes butyl acrylate/methylmethacrylate copolymer (Tg-2 DEG C) core section, and Cationic amine containing shell section；FLEX8300TMIt is the propylene that the method according to U.S. Patent No. 7,674,860 is manufactured Sour (co) polymer RDP.
These results indicate with comprising acrylic based emulsion powder and the preferably conventional texture coating of acrylic based emulsion Preparation is compared, and veining coatings formulation of the invention provides improved DPUR.
Wet abrasive resistance (" scouring ") result of 70%PVC veining coatings formulations is summarized in table 7 below .1 to 7.5：
Table 7.1：Redox polymerize with thermal initiation
(without using chain-transferring agent in any one of these examples)
Table 7.2：The weight ratio of alkali soluble resins outer portion part and inner section
(without using chain-transferring agent in any one of these examples)
Table 7.3：Polyfunctional monomer in copolymer inner section
(without using chain-transferring agent in any one of these examples)
* clean is tested under 40 DEG C/85%RH
Table 7.4：Chain-transferring agent
Table 7.5：Extra water-repelling agent
(without using chain-transferring agent in any one of these examples)
*SLS=NaLSs
For the wet abrasive resistance performance of veining coating and conventional texture coating relatively more of the invention, make comprising commercially available DRYCRYLTM DP DP 2903、ELOTEXTMWR8600 and ELOTEXTMFLEX8300 acrylic acid RDP or RHOPLEXTM The comparison coatings formulation determined above of EI-2000 acrylate copolymer latexes is subjected to resistance to those identicals in detail above Wet-milling is tested, and its result is summarized in table 7 below .6：
Table 7.6：Compare wet abrasive resistance result
1Dow Chemical company (The Dow Chemical Company, USA)；EI-2000 is that Tg is+12 DEG C 100% acrylate copolymer latex；DP-2903 is that Tg is+10 DEG C of 100% acrylic acid RDP；And
2Akzo Nobel's performance chemicalses Elotex AG of Switzerland.WR 8600 is come from according to U.S. Patent No. Multistage cationic polymer made from method described in 7,674, No. 860, it includes butyl acrylate/methyl methacrylate Copolymer (Tg-2 DEG C) core section, and the cationic amine containing shell section；FLEX8300TMFrom according to U.S. Patent No. 7,674,860 The acrylic acid (co) polymer RDP of method manufacture described in number.
With the result in upper table 7.6 indicate with comprising acrylic based emulsion powder and the especially conventional texture of acrylic based emulsion Change coatings formulation to compare, veining coatings formulation of the invention provides acceptable wet abrasive resistance.In fact, the present invention Coatings formulation displaying is improved better than the wet abrasive resistance of the conventional texture coatings formulation comprising acrylic based emulsion powder, and Texture with being prepared for the liquid polymers by being specially designed in external process composition is provided in a preferred embodiment Change the suitable patience of the patience observed of coating.

Claims (6)

1. a kind of non-cementing dry-mixed preparation for external process composition, the dry-mixed preparation is included dry-mixed is matched somebody with somebody as described The gross weight meter of product, 40wt.% to 80wt.% aggregate material and 3wt.% to 30wt.% water redispersible polymer Powder (RDP), the water redispersible polymer powder includes the acrylic copolymer of multistage containing carboxyl, and it has：
(a) alkali soluble resins outer portion part and one or more inner sections；
(b) boiling point be 150 DEG C to 500 DEG C and water solubility be 3.5 or less nucleator；And
(c) deflocculant,
Wherein when being dispersed in water, one or more described inner sections use fox equation comprising glass transition temperature (Tg) (Fox equation) is calculated as outside -40 DEG C to 50 DEG C of acrylic acid (co) polymer, and wherein described alkali soluble resins The weight ratio of section and one or more inner sections is 1:19 to 2:3.
2. non-cementing dry-mixed preparation according to claim 1, it further includes one or more pigment, wherein the face Material is so that by the gross weight meter of the dry-mixed preparation, the amount no more than 10wt.% is present.
3. a kind of non-cementing external process composition, it includes dry-mixed preparation and water according to claim 1.
4. non-cementing external process composition according to claim 3, wherein the dry-mixed preparation, which is included, presses described group The dry weight meter of compound, in one or more pigment of the amount no more than 10wt.%, and wherein described processing compositions is total Pigment volume concentration (PVC) (PVC) content is 60% to 100%.
5. non-cementing external process composition according to claim 3, during it is exterior insulation and system of processing (EIFS) External coating.
6. a kind of method of use external process composition formation coating surface, methods described is included：
A) non-cementing external process composition according to claim 3 is coated on said surface；With
B) dry or allow to dry the external process composition.
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